US20030004266A1 - Pressure-sensitive adhesive compositions for surface-protecting films - Google Patents

Pressure-sensitive adhesive compositions for surface-protecting films Download PDF

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Publication number
US20030004266A1
US20030004266A1 US10/192,864 US19286402A US2003004266A1 US 20030004266 A1 US20030004266 A1 US 20030004266A1 US 19286402 A US19286402 A US 19286402A US 2003004266 A1 US2003004266 A1 US 2003004266A1
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Prior art keywords
weight
pressure
sensitive adhesive
adhesive composition
protective film
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US10/192,864
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US6902786B2 (en
Inventor
Yasuaki Kitazaki
Kinnosuke Hino
Syuji Ichimura
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NICHIBAN COMPANY Ltd FROM YASUAKI KITAZAKI KINNOSUKE HINO AND SYUJI ICHIMURA
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NICHIBAN COMPANY Ltd FROM YASUAKI KITAZAKI KINNOSUKE HINO AND SYUJI ICHIMURA
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Priority claimed from PCT/JP1996/000001 external-priority patent/WO1997025388A1/en
Application filed by NICHIBAN COMPANY Ltd FROM YASUAKI KITAZAKI KINNOSUKE HINO AND SYUJI ICHIMURA filed Critical NICHIBAN COMPANY Ltd FROM YASUAKI KITAZAKI KINNOSUKE HINO AND SYUJI ICHIMURA
Priority to US10/192,864 priority Critical patent/US6902786B2/en
Publication of US20030004266A1 publication Critical patent/US20030004266A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C08L91/08—Mineral waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • C08L93/04—Rosin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/14—Layer or component removable to expose adhesive
    • Y10T428/1471—Protective layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2861—Adhesive compositions having readily strippable combined with readily readhearable properties [e.g., stick-ons, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition for a surface-protective film, more particularly to a pressure-sensitive adhesive composition employed for a surface-protective film for protecting metal surfaces, glass surfaces, coating surfaces, etc.
  • Japanese Patent Publication No. 74627/1993 discloses a method of applying a plastic film having a pressure-sensitive adhesive layer to an adherend. According to this method, the above problems can be solved.
  • the pressure-sensitive adhesive layer is based on a hydrogenated block copolymer of styrene and a diene type hydrocarbon, so that the pressure-sensitive adhesive layer exhibits poor adhesion and poor removability against adherends and that the pressure-sensitive adhesive layer leaves stains of the adherends or leaves thereon traces of the films removed, disadvantageously.
  • the purpose of the present invention is to provide a pressure-sensitive adhesive composition for surface-protective films which is caused to exhibit excellent adhesion to adherends, not to smear the adherends nor to leave traces thereon when the films are removed from the adherends and can also impart excellent removability to surf ace-protective films.
  • the present invention relates to a pressure-sensitive adhesive composition for a surface-protective film, the composition comprising
  • the hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon employable according to the present invention preferably has a styrene content of 1 to 50% by weight and a melt flow rate (ASTM D1238, hereinafter abbreviated as MFR) of 2 to 10 g/10 minutes at 230° C. under a load of 2.16 kg.
  • MFR melt flow rate
  • the styrene content is less than 1% by weight, the resulting resin comes to have poor thermoplasticity, whereas if it is more than 50% by weight, the resulting copolymer comes to exhibit poor adhesion to adherends and to have an increased modulus of elasticity and reduced compatibility with the tackifier resin or the softener, so that such random copolymers having styrene contents not within the specified range are not preferred as components of pressure-sensitive adhesives for surface-protective films.
  • the diene type hydrocarbon to be employed as a comonomer includes, for example, isoprene and butadiene, etc.
  • Tackifier resins employable include petroleum aliphatic resins, alicyclic resins, rosin resins, terpene resins, etc., particularly preferably hydrogenated resins thereof in view of weathering resistance.
  • Softening agents employable include oils, paraffin waxes, low-molecular weight polybutenes, low-molecular weight polyisoprenes, stearic acid, etc.
  • the pressure-sensitive adhesive composition if the amount of hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon is less than 40% by weight and the amount of tackifier resin or the softener is more than 60% by weight, the resulting composition comes to exhibit poor adhesion to adherends and smears them or leave traces thereon, unpractically, when surface-protective films are removed from the adherend.
  • the pressure-sensitive adhesive composition for surface-protective films of the present invention may, as necessary, be incorporated with a filler or a lubricant such as talc, stearic acid amide and calcium stearate; a pigment or a dye such as titanium dioxide; a reinforcing material, for example, inorganic hollow particles such as glass balloon and silica balloon; a microspherical polymer, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, etc., so long as the objective of the present invention is not impaired.
  • a filler or a lubricant such as talc, stearic acid amide and calcium stearate
  • a pigment or a dye such as titanium dioxide
  • a reinforcing material for example, inorganic hollow particles such as glass balloon and silica balloon
  • a microspherical polymer an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, etc.
  • Base materials employable in the surface-protective films having the pressure-sensitive adhesive compositions of the present invention include known plastic films such as of a polyethylene film, a polypropylene film, a polyester film, nylon and polyvinyl chloride; or such films incorporated with a filler or a pigment such as talc, calcium carbonate and titanium dioxide by means of kneading; and paper, fabric and printed matters thereof.
  • the resulting melt was applied to a 60 ⁇ m-thick base film consisting of 100 parts of polypropylene (trade name: IDEMITSU POLYPRO F-700N, available from Idemitsu Petrochemical Co., Ltd.); 0.1 part of a benzotriazole ultraviolet absorber (trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.); and 0.1 part of a hindered phenol antioxidant (trade name: IRGANOX 1010, available from Ciba-Geigy Japan, Ltd.) to a thickness of 20 ⁇ m by means of extrusion coating.
  • polypropylene trade name: IDEMITSU POLYPRO F-700N, available from Idemitsu Petrochemical Co., Ltd.
  • a benzotriazole ultraviolet absorber trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.
  • IRGANOX 1010 a hindered phenol antioxidant
  • a pressure-sensitive adhesive composition which is a blend of 90% by weight of a hydrogenated block copolymer consisting of 13% by weight of styrene and 87% by weight of butadiene (trade name: KRATON G1657, available from Shell Japan) and 10% by weight of a hydrogenated petroleum resin (trade name: I-MARV P-100, available from Idemitsu Petrochemical Co., Ltd.) was melted with heating. The resulting melt was applied to the same base film as used in Example 1 to a thickness of 20 ⁇ m by means of extrusion coating.
  • the surface-protective films employing the pressure-sensitive adhesive compositions of the present invention showed excellent adhesion to adherends and excellent weathering resistance, and they also showed removability from the adherends and did not leave stains the adherends nor left traces of the films removed.
  • the pressure-sensitive adhesive composition containing the hydrogenated block copolymer consisting of styrene and a diene type hydrocarbon as an elastomer component like in Comparative Example 2 it showed poor adhesion to the adherends and it also showed poor removability after the carbon arc irradiation, left stains of the adherends and left traces when the films were removed, so that such pressure-sensitive adhesive compositions are not suitable as pressure-sensitive adhesives for surface-protective films.
  • the pressure-sensitive adhesive composition for surface-protective films according to the present invention is caused to exhibit excellent adhesion to adherends, not to leave stains of the adherends nor to leave traces thereon when the films are removed from the adherends, because of the hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon incorporated as an elastomer component, and can also impart excellent removability to surface-protective films.
  • surface-protective films employing the pressure-sensitive adhesive compositions of the present invention exhibit excellent adhesion to coating films, stainless steel sheets, glass plates, etc. and also show excellent removability after carbon arc irradiation, the films can be applied to and removed from adherends easily and can also be used repeatedly. In addition, these films have excellent properties as surface-protective films since they do not leave stains of adherends nor leave traces after they are removed.
  • the pressure-sensitive adhesive compositions of the present invention are thermoplastic, they can be applied to base materials by means of melt extrusion using a T-die or extrusion coating as well as melt spread-coating. Further, if a base material of a thermoplastic composition is selected, a surface-protective film can be formed by a single step by co-extruding hot melts of raw material resins. Accordingly, the step of forming a film on the base material and the step of applying the pressure-sensitive adhesive to the base material can be carried out simultaneously.

Abstract

The present invention relates to a pressure-sensitive adhesive composition for a surface-protective film, the composition comprising 40% by weight or more of a hydrogenated random copolymer consisting of 1 to 50% by weight of styrene and 99 to 50% by weight of a diene type hydrocarbon and 60% by weight or less of a tackifier resin and/or a softener, and when the pressure-sensitive adhesive composition of the present invention is applied to the surface-protective film, the composition is caused to exhibit excellent adhesion to adherends, not to leave stains of the adherends nor to leave traces thereon when the films are removed from the adherends and can also impart excellent removability to surface-protective films.

Description

    TECHNICAL FIELD
  • The present invention relates to a pressure-sensitive adhesive composition for a surface-protective film, more particularly to a pressure-sensitive adhesive composition employed for a surface-protective film for protecting metal surfaces, glass surfaces, coating surfaces, etc. [0001]
    • BACKGROUND ART
  • Conventional methods for protecting surfaces of top coatings formed as finish coatings on the surfaces of vehicles include coating thinly with paraffin wax. However, this method involves a problem in that the paraffin wax coating does not exhibit sufficient protecting function and that it costs much time and labor when the paraffin wax coating is to be removed. [0002]
  • Meanwhile, Japanese Patent Publication No. 74627/1993 discloses a method of applying a plastic film having a pressure-sensitive adhesive layer to an adherend. According to this method, the above problems can be solved. In this case, however, the pressure-sensitive adhesive layer is based on a hydrogenated block copolymer of styrene and a diene type hydrocarbon, so that the pressure-sensitive adhesive layer exhibits poor adhesion and poor removability against adherends and that the pressure-sensitive adhesive layer leaves stains of the adherends or leaves thereon traces of the films removed, disadvantageously. [0003]
  • The purpose of the present invention is to provide a pressure-sensitive adhesive composition for surface-protective films which is caused to exhibit excellent adhesion to adherends, not to smear the adherends nor to leave traces thereon when the films are removed from the adherends and can also impart excellent removability to surf ace-protective films. [0004]
    • DISCLOSURE OF THE INVENTION
  • The present invention relates to a pressure-sensitive adhesive composition for a surface-protective film, the composition comprising [0005]
  • 40% by weight or more of a hydrogenated random copolymer consisting of 1 to 50% by weight of styrene and 99 to 50% by weight of a diene type hydrocarbon, and [0006]
  • 60% by weight or less of a tackifier resin and/or a softener. [0007]
    • BEST MODE FOR CARRYING OUT THE INVENTION
  • The present invention will be explained below specifically. [0008]
  • The hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon employable according to the present invention preferably has a styrene content of 1 to 50% by weight and a melt flow rate (ASTM D1238, hereinafter abbreviated as MFR) of 2 to 10 g/10 minutes at 230° C. under a load of 2.16 kg. If the styrene content is less than 1% by weight, the resulting resin comes to have poor thermoplasticity, whereas if it is more than 50% by weight, the resulting copolymer comes to exhibit poor adhesion to adherends and to have an increased modulus of elasticity and reduced compatibility with the tackifier resin or the softener, so that such random copolymers having styrene contents not within the specified range are not preferred as components of pressure-sensitive adhesives for surface-protective films. [0009]
  • The diene type hydrocarbon to be employed as a comonomer includes, for example, isoprene and butadiene, etc. [0010]
  • Tackifier resins employable include petroleum aliphatic resins, alicyclic resins, rosin resins, terpene resins, etc., particularly preferably hydrogenated resins thereof in view of weathering resistance. [0011]
  • Softening agents employable include oils, paraffin waxes, low-molecular weight polybutenes, low-molecular weight polyisoprenes, stearic acid, etc. [0012]
  • In the pressure-sensitive adhesive composition, if the amount of hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon is less than 40% by weight and the amount of tackifier resin or the softener is more than 60% by weight, the resulting composition comes to exhibit poor adhesion to adherends and smears them or leave traces thereon, unpractically, when surface-protective films are removed from the adherend. [0013]
  • The pressure-sensitive adhesive composition for surface-protective films of the present invention may, as necessary, be incorporated with a filler or a lubricant such as talc, stearic acid amide and calcium stearate; a pigment or a dye such as titanium dioxide; a reinforcing material, for example, inorganic hollow particles such as glass balloon and silica balloon; a microspherical polymer, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, etc., so long as the objective of the present invention is not impaired. [0014]
  • Base materials employable in the surface-protective films having the pressure-sensitive adhesive compositions of the present invention include known plastic films such as of a polyethylene film, a polypropylene film, a polyester film, nylon and polyvinyl chloride; or such films incorporated with a filler or a pigment such as talc, calcium carbonate and titanium dioxide by means of kneading; and paper, fabric and printed matters thereof.[0015]
    • EXAMPLES
  • The present invention will be explained more specifically by way of Examples. It should be noted that expressions “part(s)” all mean “part(s) by weight.”[0016]
    • Example 1
  • A pressure-sensitive adhesive composition containing 100 parts of a blend of 90% by weight of a hydrogenated random copolymer consisting of 10% by weight of styrene and 90% by weight of butadiene (trade name: DYNARON 1320P, available from Japan Synthetic Rubber Co., Ltd.) and 10% by weight of a hydrogenated terpene resin (trade name: CLIALON M-105, available from Yasuhara Chemical Co., Ltd.); 0.1 part of a benzotriazole ultraviolet absorber (trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.); and 0.1 part of a hindered phenol antioxidant (trade name: IRGANOX 565, available from Ciba-Geigy Japan, Ltd.) was melted with heating. The resulting melt was applied to a 60 μm-thick base film consisting of 100 parts of polypropylene (trade name: IDEMITSU POLYPRO F-700N, available from Idemitsu Petrochemical Co., Ltd.); 0.1 part of a benzotriazole ultraviolet absorber (trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.); and 0.1 part of a hindered phenol antioxidant (trade name: IRGANOX 1010, available from Ciba-Geigy Japan, Ltd.) to a thickness of 20 μm by means of extrusion coating. [0017]
    • Example 2
  • A pressure-sensitive adhesive composition containing 100 parts of a blend of 60% by weight of a hydrogenated random copolymer consisting of 10% by weight of styrene and 90% by weight of butadiene (trade name: DYNARON 1320P, available from Japan Synthetic Rubber Co., Ltd.) and 40% by weight of a hydrogenated petroleum resin (trade name: I-MARV P-100, available from Idemitsu Petrochemical Co., Ltd.); 0.05 part of a benzotriazole ultraviolet absorber (trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.); and 0.1 part of a hindered phenol antioxidant (trade name: IRGANOX 565, available from Ciba-Geigy Japan, Ltd.) was melted with heating. The resulting melt was applied to the similar base film as used in Example 1 to a thickness of 20 μm by means of extrusion coating. [0018]
    • Example 3
  • A pressure-sensitive adhesive composition containing 100 parts of a blend of 80% by weight of a hydrogenated random copolymer consisting of 30% by weight of styrene and 70% by weight of butadiene (trade name: DYNARON 1910P, available from Japan Synthetic Rubber Co., Ltd.), 10% by weight of a hydrogenated petroleum resin (trade name: ESCOREZ 5300, available from TONEX) and 10% by weight of a liquid polyisoprene (trade name: LIR-30, available from Kuraray Co., Ltd.); 0.1 part of a benzotriazole ultraviolet absorber (trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.); and 0.1 part of a hindered phenol antioxidant (trade name: IRGANOX 565, available from Ciba-Geigy Japan, Ltd.) was melted with heating. The resulting melt was applied to the same base film as used in Example 1 to a thickness of 20 μm by means of extrusion coating. [0019]
    • Comparative Example 1
  • A pressure-sensitive adhesive composition containing 100 parts of a blend of 20% by weight of a hydrogenated random copolymer consisting of 10% by weight of styrene and 90% by weight of butadiene (trade name: DYNARON 1320P, available from Japan Synthetic Rubber Co., Ltd.) and 80% by weight of a hydrogenated terpene resin (trade name: CLIALON M-105, available from Yasuhara Chemical Co., Ltd.); 0.05 part of a benzotriazole ultraviolet absorber (trade name: TINUVIN P, available from Ciba-Geigy Japan, Ltd.); and 0.05 part of a hindered phenol antioxidant (trade name: IRGANOX 565, available from Ciba-Geigy Japan, Ltd.) was melted with heating. The resulting melt was applied to the similar base film as used in Example 1 to a thickness of 20 μm by means of extrusion coating. [0020]
    • Comparative Example 2
  • A pressure-sensitive adhesive composition which is a blend of 90% by weight of a hydrogenated block copolymer consisting of 13% by weight of styrene and 87% by weight of butadiene (trade name: KRATON G1657, available from Shell Japan) and 10% by weight of a hydrogenated petroleum resin (trade name: I-MARV P-100, available from Idemitsu Petrochemical Co., Ltd.) was melted with heating. The resulting melt was applied to the same base film as used in Example 1 to a thickness of 20 μm by means of extrusion coating. [0021]
  • The surface-protective films obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied to coated surfaces, stainless steel sheets and glass plates to test their adhesion properties to the adherends and weathering resistance. It should be noted here that weathering resistance of each film was tested after carbon arc irradiation for 60 hours in a weatherometer in terms of removability, the degree of leaving stains occurred in the adherend after removal of the film and presence or absence of trace of the films removed. [0022]
  • The test results are shown in Table 1. [0023]
    TABLE 1
    Adhesion to
    adherend Weathering resistance
    surfaces Removability Stains Trace
    Example 1 Good Good Nil Nil
    Example 2 Good Good Nil Nil
    Example 3 Good Good Nil Nil
    Comp. Poor Good Occurred Occurred
    Example 1
    Comp. Poor Poor Occurred Occurred
    Example 2
  • Adhesion to Adherend Surfaces: [0024]
  • Adhesion to coating film, stainless steel sheet and glass plate surfaces [0025]
  • Removability, Stains and Trace: [0026]
  • Evaluated after 60-hours carbon arc irradiation in a weatherometer [0027]
  • As is clear from the results of Examples 1 to 3 in Table 1, the surface-protective films employing the pressure-sensitive adhesive compositions of the present invention showed excellent adhesion to adherends and excellent weathering resistance, and they also showed removability from the adherends and did not leave stains the adherends nor left traces of the films removed. [0028]
  • Meanwhile, in the case of the pressure-sensitive adhesive composition containing less than 40% by weight of the hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon like in Comparative Example 1, it showed poor adhesion to the adherends and it also smeared the adherends and left traces of the films removed, so that such pressure-sensitive adhesive compositions are not suitable as pressure-sensitive adhesives for surface-protective films. [0029]
  • Further, in the case of the pressure-sensitive adhesive composition containing the hydrogenated block copolymer consisting of styrene and a diene type hydrocarbon as an elastomer component like in Comparative Example 2, it showed poor adhesion to the adherends and it also showed poor removability after the carbon arc irradiation, left stains of the adherends and left traces when the films were removed, so that such pressure-sensitive adhesive compositions are not suitable as pressure-sensitive adhesives for surface-protective films. [0030]
    • INDUSTRIAL APPLICABILITY
  • The pressure-sensitive adhesive composition for surface-protective films according to the present invention is caused to exhibit excellent adhesion to adherends, not to leave stains of the adherends nor to leave traces thereon when the films are removed from the adherends, because of the hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon incorporated as an elastomer component, and can also impart excellent removability to surface-protective films. [0031]
  • In other words, since surface-protective films employing the pressure-sensitive adhesive compositions of the present invention exhibit excellent adhesion to coating films, stainless steel sheets, glass plates, etc. and also show excellent removability after carbon arc irradiation, the films can be applied to and removed from adherends easily and can also be used repeatedly. In addition, these films have excellent properties as surface-protective films since they do not leave stains of adherends nor leave traces after they are removed. [0032]
  • Meanwhile, since the pressure-sensitive adhesive compositions of the present invention are thermoplastic, they can be applied to base materials by means of melt extrusion using a T-die or extrusion coating as well as melt spread-coating. Further, if a base material of a thermoplastic composition is selected, a surface-protective film can be formed by a single step by co-extruding hot melts of raw material resins. Accordingly, the step of forming a film on the base material and the step of applying the pressure-sensitive adhesive to the base material can be carried out simultaneously. [0033]

Claims (5)

1. A pressure-sensitive adhesive composition for a surface-protective film, the composition comprising:
40% by weight or more of a hydrogenated random copolymer consisting of 1 to 50% by weight of styrene and 99 to 50% by weight of a diene type hydrocarbon, and
60% by weight or less of a tackifier resin and/or a softener.
2. The pressure-sensitive adhesive composition for a surface-protective film according to claim 1, wherein the hydrogenated random copolymer consisting of styrene and a diene type hydrocarbon has a melt flow rate of 2 to 10 g/10 minutes measured in accordance with ASTM D1238 at 230° C. under a load of 2.16 kg.
3. The pressure-sensitive adhesive composition for a surface-protective film according to claim 1, wherein the diene type hydrocarbon is selected from isoprene and butadiene.
4. The pressure-sensitive adhesive composition according for a surface-protective film according to claim 1, wherein the tackifier resin is selected from the group consisting of petroleum aliphatic resins, alicyclic resins, rosin resins, terpene resins and hydrogenated resins thereof.
5. The pressure-sensitive adhesive composition for a surface-protective film according to claim 1, wherein the softener is selected from the group consisting of oils, paraffin waxes, low-molecular weight polybutenes, low-molecular weight polyisoprenes and stearic acid.
US10/192,864 1996-01-04 2002-07-10 Pressure-sensitive adhesive compositions for surface-protecting films Expired - Fee Related US6902786B2 (en)

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US10/192,864 US6902786B2 (en) 1996-01-04 2002-07-10 Pressure-sensitive adhesive compositions for surface-protecting films

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PCT/JP1996/000001 WO1997025388A1 (en) 1996-01-04 1996-01-04 Pressure-sensitive adhesive composition for surface protective film
US10121698A 1998-07-02 1998-07-02
US10/192,864 US6902786B2 (en) 1996-01-04 2002-07-10 Pressure-sensitive adhesive compositions for surface-protecting films

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PCT/JP1996/000001 Continuation WO1997025388A1 (en) 1996-01-04 1996-01-04 Pressure-sensitive adhesive composition for surface protective film

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040054040A1 (en) * 2002-08-12 2004-03-18 Lin Chon Yie Plasticized polyolefin compositions
US20040186214A1 (en) * 2002-08-12 2004-09-23 Wen Li Fibers and nonwovens from plasticized polyolefin compositions
US20040260001A1 (en) * 2002-08-12 2004-12-23 Lin Chon-Yie Articles from plasticized polyolefin compositions
US20050148720A1 (en) * 2002-08-12 2005-07-07 Wen Li Plasticized polyolefin compositions
US20060008643A1 (en) * 2002-08-12 2006-01-12 Lin Chon Y Polypropylene based fibers and nonwovens
US20070243341A1 (en) * 2006-04-17 2007-10-18 Nitto Denko Corporation Base material for pressure-sensitive adhesive tape or sheet, pressure-sensitive adhesive tape or sheet having light-reflective property or light-shielding property and liquid crystal display apparatus
US20080045638A1 (en) * 2002-08-12 2008-02-21 Chapman Bryan R Plasticized hetero-phase polyolefin blends
US20090312483A1 (en) * 2005-06-23 2009-12-17 Kitson Ralph P Pressure sensitive adhesive
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
US8513347B2 (en) 2005-07-15 2013-08-20 Exxonmobil Chemical Patents Inc. Elastomeric compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009113153A1 (en) * 2008-03-10 2009-09-17 ニチバン株式会社 Surface-protective sheet

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3513141A (en) * 1967-08-08 1970-05-19 Phillips Petroleum Co Process for improving ozone resistance of hydrogenated rubber
US3798190A (en) * 1966-11-03 1974-03-19 Bridgestone Tire Co Ltd Rubber blends containing an hydrogenated styrene butadiene random copolymer
US3935176A (en) * 1970-09-14 1976-01-27 The International Synthetic Rubber Co., Ltd. Thermosplastic elastomeric materials
US4102849A (en) * 1975-01-20 1978-07-25 The Firestone Tire & Rubber Company Oil-extended hydrogenated diblock copolymer
US5496601A (en) * 1994-02-14 1996-03-05 Minnesota Mining And Manufacturing Company Extensible flatback adhesive sheet
US5585443A (en) * 1994-08-23 1996-12-17 Bridgestone Corporation Block copolymer
US5610212A (en) * 1993-05-13 1997-03-11 Kao Corporation Means for mechanically stabilizing deproteinized natural rubber latex
US5965255A (en) * 1996-03-08 1999-10-12 Nichiban Company Limited Pressure-sensitive adhesive sheet for surface protection

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60123574A (en) 1983-12-07 1985-07-02 Hayakawa Rubber Co Ltd Surface-adhesive rubber sheet
JPS62127376A (en) 1985-11-27 1987-06-09 Nitto Electric Ind Co Ltd Surface protecting film
JPH0684489B2 (en) 1987-08-11 1994-10-26 三井石油化学工業株式会社 Hot melt adhesive composition
JPH0270734A (en) 1988-09-06 1990-03-09 Japan Synthetic Rubber Co Ltd Rubber composition for waterproof sheet
JPH02123173A (en) 1988-11-01 1990-05-10 Japan Synthetic Rubber Co Ltd Primer composition
JPH03223381A (en) 1990-01-30 1991-10-02 Mitsui Petrochem Ind Ltd Hot-melt self-adhesive composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798190A (en) * 1966-11-03 1974-03-19 Bridgestone Tire Co Ltd Rubber blends containing an hydrogenated styrene butadiene random copolymer
US3513141A (en) * 1967-08-08 1970-05-19 Phillips Petroleum Co Process for improving ozone resistance of hydrogenated rubber
US3935176A (en) * 1970-09-14 1976-01-27 The International Synthetic Rubber Co., Ltd. Thermosplastic elastomeric materials
US4102849A (en) * 1975-01-20 1978-07-25 The Firestone Tire & Rubber Company Oil-extended hydrogenated diblock copolymer
US5610212A (en) * 1993-05-13 1997-03-11 Kao Corporation Means for mechanically stabilizing deproteinized natural rubber latex
US5496601A (en) * 1994-02-14 1996-03-05 Minnesota Mining And Manufacturing Company Extensible flatback adhesive sheet
US5585443A (en) * 1994-08-23 1996-12-17 Bridgestone Corporation Block copolymer
US5965255A (en) * 1996-03-08 1999-10-12 Nichiban Company Limited Pressure-sensitive adhesive sheet for surface protection

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8003725B2 (en) 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
US20040260001A1 (en) * 2002-08-12 2004-12-23 Lin Chon-Yie Articles from plasticized polyolefin compositions
US20100152346A1 (en) * 2002-08-12 2010-06-17 Henry Wu-Hsiang Yang Plasticized Polyolefin Compositions
US20050148720A1 (en) * 2002-08-12 2005-07-07 Wen Li Plasticized polyolefin compositions
US20060008643A1 (en) * 2002-08-12 2006-01-12 Lin Chon Y Polypropylene based fibers and nonwovens
US20100035498A1 (en) * 2002-08-12 2010-02-11 Lundmark Bruce R Plasticized Polyolefin Compositions
US20080045638A1 (en) * 2002-08-12 2008-02-21 Chapman Bryan R Plasticized hetero-phase polyolefin blends
US20080070994A1 (en) * 2002-08-12 2008-03-20 Wen Li Fibers and Nonwovens from Plasticized Polyolefin Compositions
US7875670B2 (en) 2002-08-12 2011-01-25 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
US8217112B2 (en) 2002-08-12 2012-07-10 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US8211968B2 (en) 2002-08-12 2012-07-03 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US20040186214A1 (en) * 2002-08-12 2004-09-23 Wen Li Fibers and nonwovens from plasticized polyolefin compositions
US20090171001A1 (en) * 2002-08-12 2009-07-02 Lin Chon-Yie Articles from Plasticized Polyolefin Compositions
US7985801B2 (en) 2002-08-12 2011-07-26 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
US7998579B2 (en) 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US20040054040A1 (en) * 2002-08-12 2004-03-18 Lin Chon Yie Plasticized polyolefin compositions
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8703030B2 (en) 2003-08-12 2014-04-22 Exxonmobil Chemical Patents Inc. Crosslinked polyethylene process
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
US20090312483A1 (en) * 2005-06-23 2009-12-17 Kitson Ralph P Pressure sensitive adhesive
US8513347B2 (en) 2005-07-15 2013-08-20 Exxonmobil Chemical Patents Inc. Elastomeric compositions
US20070243341A1 (en) * 2006-04-17 2007-10-18 Nitto Denko Corporation Base material for pressure-sensitive adhesive tape or sheet, pressure-sensitive adhesive tape or sheet having light-reflective property or light-shielding property and liquid crystal display apparatus

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